Conditions for quantitative analysis of the mixture of saturated fatty acid mono-, di- and triglycerides were examined. The results were as follows : 1) The analysis should be carried out under constant room temperature and low relative humidity, because the spots of TLC exuded and reliable results could not obtain under high relative humidity and high room temperature, such as in summer. 2) Easiness in the exudation of spots was observed in the following sequence; 1, 2-dilaurin> 1, 3-dilaurin, 1-monolaurin, 2-monolaurin>trilaulin, methyl laurate, lauric acid. 3) The optimum conditions for quantitative analysis were as follows : Developing solvents; Benzene-methanol (98 : 2vol/vol) for partial glycerides, and benzene for triglycerides and for fatty acid esters. Activation temperature and time : 110140°C, 30min. Detection agent : 5%-phosphomoribdic acid in ethanol. Charring temperature and time : 200°C, 10min. Standing time after charring : from 20 to 240min. Relative humidity : below 53% (rainy and summer season) 4) The mixtures of 1-monolaurin, 1, 2-dilaurin, 1, 3-dilaurin and trilaurin were analyzed under the above optimum conditions and reliable results were obtained.
The compositions of sterols of snails and bivalves were determined. In this study, six species of marine snails, two species of fresh-water snails, two species of marine bivalves, fresh-water and brackish-water bivalve were examined. The unsaponifiable matter was acetylated and separated in to several fractions by silver nitrateimpregnated silicic acid column chromatography. Sterol composition of each fraction was determined by GLC. It was shown that the sterol composition of snails, fresh-water and brackish-water bivalves is different from that of marine bivalves. Cholesterol was 7090% in snails, 6070% in fresh-water and brackish-water bivalves, and 3040% in marine bivalves. UV absorption spectra showed the presence of Δ5, 7-sterol in these mollusks, and 7-dehydrochole-sterol was isolated. C29-sterols showed the difference with the species of mollusks.
1) Authors found that lecithin region appears as two spots (upper spot; Lec (U), lower spot; Lec (L)), on sillica gel plate which developed in a mixture of n-butanol : acetic acid : water (60 : 20 : 20). 2) It was suggested that these chromatographic patterns of lecithin region were caused by some minor contaminations contained in adsorbents. 3) White crystalline substance was obtained from silica gel adsorbent as a major component of extraction with chloroform : methanol : acetic acid (2 : 1 : 1), and it was identified as sodium acetate. 4) As a result, it was found that sodium silicate, sodium carbonate and sodium bicarbonate had similar effects on the silica gel plates for lecithin, but sodium chloride, sodium sulfate, calcium chloride and calcium sulfate had no effect. 5) Sphingomyelin and lyso-lecithin also appeared as two spots such as lecithin on silica gel plates containing sodium acetate with the above developing solvent. Moreover, lyso-lecithin of ten appeared as two spots on silica gel plates containing sodium acetate developed with a mixture of diisobutylketone : acetic acid : water (40 : 25 : 5).
Thermostability of the natural tocopherol mixture was compared with that of Butylated hydroxyanisole by using the continuous water-spraying and heating system. In the frying conditions, thermostability mainly depends on the stability to the volatilization by steaming and this is a very important property of antioxidants which are used in frying oils. The test was carried out under condition that the fat surface in the system was protected from the air by means of metal float and the thermal oxidative deterioration was thus prevented as far as possible. As a result, tocopherol showed a better stability, that is, the rates of decrease of its content and of the induction period of heated oils were very small as compared with that of butylated hydroxyanisole. On the other hand, as shown in Fig.-2, rapid decrease of tocopherol content which might be mainly caused by thermal oxidation, was observed in parallel with the decrease of the induction period of heated oils when the fat surface was kept to be exposed to air. As mentioned above, it was recognized that when thermal oxidative deterioration during frying was maintained as minimal as possible, natural tocopherol mixture was a suitable antioxidant for frying oils.
Rate constant of Diels-Alder addition reaction of maleic anhydride or dimethyl maleate to methyl trans-9, trans-11-octadecadienoate was determined. From the results of rate measurement, the dienophilic activity of maleic anhydride was observed to be about one thousand times as great as that of methyl acrylate. On the other hand, the dienophilic activity of dimethyl maleate was only about one-third of methyl acrylate. The maleic anhydride adduct (mp 72.473.2°C) recrystallized from n-heptane was confirmed to be the endo configuration by NMR analysis. The addition reaction of dimethyl maleate to the octadecadienoate gave cyclic adducts, and NMR, IR, and MS spectral analyses of the adducts showed that they were a mixture of the endo adduct of dimethyl maleate which had the same configuration as that of methyl ester derived from the maleic anhydride adduct and, presumably, the adduct of dimethyl fumarate, which would be formed by thermal isomerization of dimethyl maleate during the addition reaction.
Singly γ-carboxypropylated compounds [sample number (7) and (8)] were prepared by the partial OH-carboxypropylation reaction of 6, 6'-dihydroxy 3, 3'-dimethyl-diphenylmethane (2) and 2, 6-bis (2-hydroxy-5-methylbenzyl) -p-cresol (3) with γ-butyrolactone. Beside the above two samples; (4), (5) and (6), which were completely γ-carboxypropylated products derived from p-cresol (1), (2) and (3) as reported in the previous paper, were used as the comparative sample in order to test the surface active properties. The properties of (7) and (8) were measured and compared with other samples (4) (6). Results obtained were as follows. 1) Among the samples studied, only (8) exhibited a considerable decrease in the surface tension and a promotion in the solubilization of Orange OT and in the emulsification of liquid paraffin in water. 2) Studies on the surface tension, solubilization of dye and electrolytic conductivity as a function of concentration of the samples, indicated that the samples (7) and (8) form a micelle, but other compounds (4) (6) do not form micelle.
The effects of acid salts (NaHCO3, NaHSO4, NaHSO3 and Na2HPO4) on the reaction of lauryl chloride (RCl) with sodium hydrogensulfide (NaSH) in n-butanol were investigated. Acid salts react with NaSH to generate hydrogensulfide (H2S), which may react with sodium sulfide (Na2S) to yield NaSH. As a whole, the effect of acid salts depends on the following reaction : Na2S+NaHSO3→Na2SO3+NaSH The yield of lauryl mercaptan and the amount of distillation residue were nearly the same as the case of addition of H2S presented in the previous paper. The amounts of water and NaSH did not give so much influence on the yield of mercaptan, but the reaction rate decreased with increasing amount of water. A considerable amount of disulfide (RSSR) formed even in the n-butanol. In the absence of H2S or acid salts, it was presumed that the following reaction occurred :
The alkyl composition of alkyl-polyglycolethersulfate was determined by the reaction of Alfol12, 14 alcohol polyglycolate with hydroiodic acid. Alkyliodide formed was separated by gas-liquid chromatography, and the higher alcohol composition was calculated satisfactorily from the content of each alkyliodide. The method was applied to the analysis of commercial liquid shampoos.
It was found that commercial filter papers contained appreciable amount of organic solvent extractable, non-volatile substances (abbreviated as impurities). The contents and some chemical properties of the impurities obtained from several kinds of commercial filter paper products were examined by means of gravimetric analysis, thin-layer chromatography, gas liquid chromatography and infra-red spectroscopy. There were about 0.040.08 weight per cent impurities (a filter paper piece of 9cm diam. contains about 200400μg impurities), whose major components were complex mixture of C16C33 saturated and unsaturated hydrocarbon having straight and branched structures.